JP4070366B2 - Optical recording material - Google Patents

Description

【化４】

【００１６】
また、本発明は、基体上に、記録層として上記光学記録材料を含有する薄膜を形成したことを特徴とする光学記録媒体を提供するものである。
【００１７】
【発明の実施の形態】
以下、本発明の光学記録材料について詳細に説明する。
【００１８】
本発明の光学記録材料に用いられる上記一般式（Ｉ）で表される化合物は、新規の化合物であり、後述の光学記録媒体の記録層に使用される機能性付与添加剤である。
【００１９】
上記一般式（Ｉ ' ）において、環Ａ中のＲ₁で表されるハロゲン原子としては、例えば、フッ素、塩素、臭素、ヨウ素が挙げられ、炭素数１〜４のアルキル基としては、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、第二ブチル、第三ブチル等が挙げられ、炭素数１〜４のアルコキシ基としては、上記アルキル基から誘導される基が挙げられ、Ｒで表される炭素数１〜３０の有機基は特に制限を受けず、枝分かれ、不飽和結合、エーテル結合、アリール基等を含んでいても良く、ハロゲン原子、シアノ基、ニトロ基等の置換基を有していても良い基が挙げられ、Ｙで表される炭素数１〜６のアルキリデン基としては、メチリデン、ジメチルメチリデン、エチルメチルメチリデン、ジエチルメチリデン、メチルプロピルメチリデン、エチルプロピルメチリデン等が挙げられ、炭素数３〜６のシクロアルキリデンとしては、シクロプロパン−１，１−ジイル、シクロブタン−１，１−ジイル、２，４−ジメチルシクロブタン−１，１−ジイル、３−ジメチルシクロブタン−１，１−ジイル、シクロペンタン−１，１−ジイル、シクロヘキサン−１，１−ジイル等が挙げられ、炭素数１〜８のアルキル基を有する窒素原子における該アルキル基としては、メチル、エチル、プロピル、イソプロピル、ブチル、第二ブチル、第三ブチル、イソブチル、アミル、第三アミル、ヘキシル、へプチル、オクチル、イソオクチル、第三オクチル、２−エチルヘキシル等が挙げられる。
【００２０】
上記一般式（Ｉ ' ）において、Ａｎ^m-で表されるアニオンは、特に制限を受けないが、例えば、塩素アニオン、臭素アニオン、ヨウ素アニオン、フッ素アニオン等のハロゲンアニオン；過塩素酸アニオン、塩素酸アニオン、チオシアン酸アニオン、六フッ化リンアニオン、六フッ化アンチモンアニオン、四フッ化ホウ素アニオン等の無機系アニオン、ベンゼンスルホン酸アニオントルエンスルホン酸アニオン、トリフルオロメタンスルホン酸アニオン等の有機スルホン酸アニオン；オクチルリン酸アニオン、ドデシルリン酸アニオン、オクタデシルリン酸アニオン、フェニルリン酸アニオン、ノニルフェニルリン酸アニオン、２，２' −メチレンビス（４，６−ジ第三ブチルフェニル）ホスホン酸アニオン等の有機リン酸系アニオン、後述のクエンチャーアニオン等が挙げられ、二価のものとしては、例えば、ベンゼンジスルホン酸アニオン、ナフタレンジスルホン酸アニオン等が挙げられる。
【００２１】
また、上記一般式（Ｉ ' ）において、Ｘで表されるメタロセン基は、下記〔化５〕で表されるフェロセン基であり、公知一般のフェロセン化合物から導入できる。
【００２２】
【化５】

【００２４】
上記一般式（Ｉ ' ）で表される化合物は、詳しくは下記〔化６〕（前記〔化１〕と同じ）の一般式（Ｉ）で表される化合物であり、該化合物はコスト及び性能の点で好ましい。
【００２５】
【化６】

【００２６】
上記一般式（Ｉ）において、Ｒ₁ 、Ｒ、Ｙで表される基及びＡｎ^m-としては、前記の一般式（Ｉ ' ）と同様のものが挙げられる。
【００２７】
上記一般式（Ｉ）で表される化合物の具体例としては、下記化合物Ｎｏ．１〜Ｎｏ．８等が挙げられる。尚、以下の例示では、アニオンを省いたカチオンで示している。
【００２８】
【化７】

【００２９】
【化８】

【００３０】
【化９】

【００３１】
【化１０】

【００３２】
【化１１】

【００３３】
【化１２】

【００３４】
【化１３】

【００３５】
【化１４】

【００３６】
更に好適な化合物としては、上記一般式（Ｉ）中のＹで表される基が炭素数１〜６のアルキリデン基又は炭素数３〜６のシクロアルキリデン基であり、Ｒで表される有機基が下記〔化１５〕（前記〔化２〕と同じ）の一般式（ II ）で表される基であるフェロセン化合物が挙げられる。
【００３７】
【化１５】

【００３８】
上記一般式（ II ）において、Ｒ₂ で表される炭素数１〜４のアルキレン基としては、例えば、メチレン、エチレン、プロピレン、１−メチルエチレン、２−メチルエチレン、ブチレン等が挙げられ、Ｒ₃ で表される炭素数１〜４のアルキル基としては、前記一般式（Ｉ）中のＲ₁ と同様の基が挙げられ、炭素数２〜４のアルケニル基としては、ビニル、プロペニル、イソプロペニル、ブテニル等が挙げられ、Ｒ₃ 中のフェニル基の置換基であるハロゲン原子としてはフッ素、塩素、臭素、ヨウ素が挙げられ、Ｒ₃ 中のフェニル基の置換基である炭素数１〜４のアルキル基、アルコキシ基としては前記一般式（Ｉ）中のＲ₁ と同様の基が挙げられる。
【００３９】
上記の更に好適な化合物の具体例としては、下記化合物Ｎｏ．９〜Ｎｏ．１４等が挙げられる。尚、以下の例示では、アニオンを省いたカチオンで示している。
【００４０】
【化１６】

【００４１】
【化１７】

【００４２】
【化１８】

【００４３】
【化１９】

【００４４】
【化２０】

【００４５】
【化２１】

【００４６】
上記で表される好適なフェロセン誘導体化合物の製造方法については、特に制限されないが、例えば、下記〔化２２〕に示すルートで合成される。
【００４７】
【化２２】

【００４８】
本発明に用いられる新規な化合物である上記一般式（Ｉ）で表される化合物（メタロセン誘導体化合物）は、以下に示す特性を有し、光学記録材料の多機能添加剤として優れた化合物である。
（１）光安定剤として機能する。
色素の自然光による褪色を防止し、記録材料に耐光性を与える。
（２）ピット形成促進剤として機能する。
色素層のピット形成温度を低温側にシフトさせる効果がある。
（３）ピット制御剤として機能する。
温度についてピット形成の明確なしきい値を与えるので、シャープなピットを形成できる。
（４）揮散性がない。
揮発性がないので、記録層形成時の安全性、品質安定性に優れる。
【００４９】
本発明の光学記録材料においては、通常、色素が使用され、該色素は、半導体レーザーによってピットを形成することのできる有機化合物系の色素であれば特に制限されず、アゾ系色素、フタロシアニン系色素及びシアニン系色素等公知のものいずれもが使用できるが、シアニン系色素が好ましく、その中でもインドシアニン系色素が優れた添加効果が得られるのでより好ましい。
【００５０】
上記色素について特に好適な具体例としては、下記化合物Ｎｏ．１５〜２３等が挙げられる。尚、以下の例示では、アニオンを省いたカチオンで示している。
【００５１】
【化２３】

【００５２】
【化２４】

【００５３】
【化２５】

【００５４】
【化２６】

【００５５】
【化２７】

【００５６】
【化２８】

【００５７】
【化２９】

【００５８】
【化３０】

【００５９】
【化３１】

【００６０】
本発明の光学記録材料は、上記メタロセン誘導体化合物〔上記一般式（Ｉ）で表される化合物〕を必須成分として含むものであり、好ましくは色素と上記メタロセン誘導体化合物の両方を含むものであり、ＬＤ、ＣＤ、ＤＶＤ、ＣＤ−Ｒ、ＤＶＤ−Ｒ等の光学記録媒体の記録層として適用される。
【００６１】
本発明の光学記録材料において、色素と上記メタロセン誘導体化合物との割合は、色素に対して上記メタロセン誘導体化合物が０．０１重量％より少ないと効果が得難いので０．０１重量％以上が好ましく、特に、ＣＤ−Ｒ、ＤＶＤ−Ｒの記録層として使用する場合は０．１〜２０重量％が好ましい。
【００６２】
次に、本発明の光学記録媒体について詳細に説明する。
本発明の光学記録媒体は、基体上に、記録層として上述した本発明の光学記録材料を含有する薄膜を形成したものである。
本発明の光学記録媒体における上記記録層の形成にあたっては従来周知の方法を用いることができる。一般には、メタノール、エタノール等の低級アルコール類、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、ブチルジグリコール等のエーテルアルコール類、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、ジアセトンアルコール等のケトン類、酢酸エチル、酢酸ブチル、酢酸メトキシエチル等のエステル類、アクリル酸エチル、アクリル酸ブチル等のアクリル酸エステル類、２，２，３，３−テトラフルオロプロパノール等のフッ化アルコール類、ベンゼン、トルエン、キシレン等の炭化水素類、メチレンジクロライド、ジクロロエタン、クロロホルム等の塩素化炭化水素類等の有機溶媒に、上記光学記録材料を溶解した溶液を基体上に塗布することによって容易に形成することができる。
【００６３】
上記記録層の厚さは、通常、０．００１〜１０μｍであり、好ましくは０．０１〜５μｍの範囲が適当である。上記記録層の形成方法は特に制限を受けず、例えばスピンコート法等の通常用いられる方法を用いることができる。
【００６４】
本発明の光学記録媒体における記録層に、上記光学記録材料を含有させる際の該記録層に対する使用量は、色素及び上記メタロセン誘導体化合物を合わせて、好ましくは５０〜１００重量％である。
【００６５】
また、本発明の光学記録媒体における上記記録層は、上記光学記録材料のほかに、必要に応じて、ポリエチレン、ポリエステル、ポリスチレン、ポリカーボネート等の樹脂類を含有してもよく、界面活性剤、帯電防止剤、滑剤、難燃剤、光安定剤、分散剤、酸化防止剤、架橋剤等を含有してもよい。
【００６６】
更に、上記記録層は、一重項酸素等のクエンチャーとして、芳香族ニトロソ化合物、ビスイミニウム塩、遷移金属キレート化合物等を含有してもよい。これらの化合物としては、例えば、特開昭５９−５５７９５号公報及び特開昭６０−２３４８９２号公報に提案されているような公知の化合物が用いられ、記録層に対して好ましくは０〜５０重量％の範囲で使用される。
【００６７】
上記クエンチャーの代表例としては、下記〔化３２〕〜〔化４０〕の一般式（Ａ）〜（Ｉ）等で表される化合物が挙げられる。
【００６８】
【化３２】

【００６９】
【化３３】

【００７０】
【化３４】

【００７１】
【化３５】

【００７２】
【化３６】

【００７３】
【化３７】

【００７４】
【化３８】

【００７５】
【化３９】

【００７６】
【化４０】

【００７７】
このような記録層を設層する上記基体の材質は、書き込み光及び読み出し光に対して実質的に透明なものであれば特に制限はなく、例えば、ポリメチルメタクリレート、ポリエチレンテレフタレート、ポリカーボネート等の樹脂、ガラス等が用いられる。また、その形状は、用途に応じ、テープ、ドラム、ベルト、ディスク等の任意の形状のものが使用できる。
【００７８】
また、上記記録層上に、金、銀、アルミニウム、銅等を用いて蒸着法或いはスパッタリング法により反射膜を形成することもできるし、アクリル樹脂、紫外線硬化性樹脂等による保護層を形成することもできる。
【００７９】
本発明の光学記録媒体の具体的態様としては、ＬＤ、ＣＤ、ＤＶＤ、ＣＤ−Ｒ、ＤＶＤ−Ｒ等の光ディスク等が挙げられる。
【００８０】
【実施例】
以下、製造例、実施例、評価例及び比較例をもって本発明を更に詳細に説明する。しかしながら、本発明は以下の実施例によって何ら制限を受けるものではない。
【００８１】
（製造例１）化合物Ｎｏ．９の六フッ化リン塩の製造
反応フラスコにベンゼンスルホニルクロリド３５．４ｇ、２−フェノキシエタノール３３．２ｇ、トルエン２２２．４ｇを仕込み、氷冷下でトリエチルアミン４０．４ｇを１時間で滴下した。冷却下で１時間反応させた後、更に室温で１時間反応させた後、水洗、無水硫酸ナトリウムでの乾燥、脱溶媒を行い得られた粗結晶についてエタノール５５．６ｇで再結晶を行い、ベンゼンスルホン酸フェノキシエチルエステル４７．２ｇ結晶を得た。（収率８５％）
次に、２，３，３−トリメチルインドレニン２３．９ｇ、上記で得られたベンゼンスルホン酸フェノキシエチルエステル４１．７ｇ、1-ブタノール１３１．２ｇを反応フラスコに仕込み、１２０℃で３時間反応させ、冷却・濾過、エタノール洗浄を行い、化合物Ｎｏ．９のベンゼンスルホン酸塩結晶５３．８ｇを得た。（収率８２％）
上記で得たベンゼンスルホン酸塩４．４ｇ、フェロセンカルボキシアルデヒド２．１ｇ、ジメチルホルムアミド６．２ｇを反応フラスコに仕込み、１時間反応させ、ヘキサフルオロリン酸カリウム塩３．７ｇ、ジメチルホルムアミド１２．４ｇを加えて８０℃で１時間塩交換させた。反応系からクロロホルム２０ｇで抽出した溶液を水洗し、無水硫酸ナトリウムで乾燥後、脱溶媒して得られた粗結晶をヘキサン／酢酸エチル＝３／７（ｖｏｌ）溶媒、シリカゲルカラムにより精製し、目的物結晶１．２ｇを得た。（収率２０％）
【００８２】
（分析結果）
ＵＶ吸収スペクトル：λmax ６４０ｎｍ（ε１．１×１０⁴ ）
ＰＭＲ吸収スペクトル（ｐｐｍ；多重度；Ｈ）
（１．８；ｓ；６）（４．４；ｓ；５）（４．５；ｔ；２）（４．８；ｔ；２）
（５．０；ｓ；２）（５．１；ｓ；２）（６．７；ｄ；２）（６．９；ｔ；１）
（７．０：ｄ；１）（７．２；ｔ；２）（７．４〜７．６；ｍ；３）
（７．６；ｄ；１）（８．３；ｄ；１）
ＭＳスペクトル：６２１（calc；６２１．３）
ＣＨＮ：Ｃ重量％；Ｈ重量％；Ｎ重量％
５８．０；４．８１；２．１４（calc；５８．０；４．８７；２．２５）
Ｆｅ分析：８．８８％（calc; ８．９９）
【００８３】
（製造例２）化合物Ｎｏ．１０のヨウ素塩の合成
反応フラスコにβ−ナフチルヒドラジン３１．６ｇ、酢酸４８．０ｇを仕込み、８０℃まで昇温して３−メチル−２−ブタノン２０．７ｇを滴下し、１００℃で２時間反応させた後、酢酸を脱溶媒した。残渣からトルエン１６７．４ｇで抽出した溶液を２０重量％水酸化ナトリウム水溶液、水で洗浄し、無水硫酸ナトリウム乾燥後脱溶媒して得られた粗結晶をトルエン４１．８ｇで再結晶し、２，３，３−トリメチルベンゾインドレニン２３．４ｇを得た。（収率５６％）
次に、上記で得られた２，３，３−トリメチルベンゾインドレニン２０．９ｇ、イソアミルアイオダイド３９．６ｇを反応フラスコに仕込み、１２０℃で３時間反応させた後、８０℃で酢酸エチル２０．４ｇを加え、晶析を行い１−イソアミル−２，３，３−トリメチルベンゾインドレニンヨウ素塩３１．３ｇを得た。（収率７７％）
上記で得たヨウ素塩４．１ｇ、フェロセンカルボキシアルデヒド２．１ｇ、ジメチルホルムアミド６．０ｇを反応フラスコに仕込み、１時間反応させて得られた粗結晶をヘキサン／酢酸エチル＝３／７（ｖｏｌ）溶媒、シリカゲルカラムで精製し目的物結晶０．７ｇを得た。（収率１２％）
【００８４】
（分析結果）
ＵＶ吸収スペクトル：λmax ６３７ｎｍ（ε１．０×１０⁴ ）
ＰＭＲ吸収スペクトル（ｐｐｍ；多重度；Ｈ）
（１．１；ｄ；６）（１．８〜１．９；ｍ；３）（１．９；ｓ；６）
（４．４；ｓ；５）（４．８；ｔ；２）（５．０；ｓ；２）（５．３；ｓ；２）
（７．２：ｄ；１）（７．６〜７．７；ｍ；３）（８．０〜８．１；ｍ；３）（８．６；ｄ；１）
ＭＳスペクトル：６０３（calc；６０３．４）
ＣＨＮ：Ｃ重量％；Ｈ重量％；Ｎ重量％
６１．４；５．６１；２．３５（calc；６１．７；５．６８；２．３２）
Ｆｅ分析：９．３０％（calc; ９．２５）
【００８５】
（製造例３）化合物Ｎｏ．１１の過塩素酸塩の合成
反応フラスコに４−メトキシフェニルヒドラジン２７．６ｇ、酢酸４８．０ｇを仕込み、８０℃まで昇温して３−メチル−２−ブタノン２０．７ｇを滴下し、１００℃で２時間反応させた後、酢酸を脱溶媒した。残渣からトルエン１５１．２ｇで抽出した溶液を２０重量％水酸化ナトリウム水溶液、水で洗浄し、無水硫酸ナトリウムで乾燥、脱溶媒して２，３，３−トリメチル−５−メトキシインドレニン２２．６ｇを得た。（収率６０％）
次に、上記で得た２，３，３−トリメチル−５−メトキシインドレニン１８．９ｇ、プロピルアイオダイド３３．８ｇを仕込み、１００℃で３時間反応させた後、８０℃で酢酸エチル１８．０ｇを加え晶析を行い、１−プロピル−２，３，３−トリメチル−５−メトキシインドレニンヨウ素塩の結晶を２６．６ｇ得た。（収率７４％）
上記で得たヨウ素塩３．６ｇ、フェロセンカルボキシアルデヒド２．１ｇ、ジメチルホルムアミド５．３ｇを反応フラスコに仕込み、１時間反応させた後過塩素酸ナトリウム一水和物２．８ｇのメタノール１１．２ｇ溶液を加えて７０℃で１時間塩交換を行った。反応液からクロロホルム２０ｇで抽出した溶液を水洗し、無水硫酸ナトリウムで乾燥、脱溶媒して得られた粗結晶をヘキサン／酢酸エチル＝３／７（ｖｏｌ）溶液、シリカゲルカラムで精製し目的物結晶０．８ｇを得た。（収率１５％）
【００８６】
（分析結果）
ＵＶ吸収スペクトル；λmax ６２５ｎｍ（ε０．９３×１０⁴ ）
ＰＭＲ吸収スペクトル（ｐｐｍ；多重度；Ｈ）
（１．０；ｔ；３）（１．９；ｓ；６）（２．０；ｍ；２）（３．９；ｓ；３）
（４．３；ｓ；５）（４．４；ｔ；２）（５．０；ｓ；２）（５．１；ｓ；２）
（６．９；ｄ；１）（７．０；ｍ；２）（７．５：ｄ；１）（８．２；ｄ；１）
ＭＳスペクトル：５２７（calc；５２７．８）
ＣＨＮ：Ｃ重量％；Ｈ重量％；Ｎ重量％
５８．９；５．６９；２，６６（calc；５９．２；５．７３；２．６５ ）
Ｆｅ分析：１０．３％（calc; １０．６）
【００８７】
（製造例４）化合物Ｎｏ．１２の四フッ化硼素塩の合成
反応フラスコに４−ニトロフェニルヒドラジン１５３．１ｇ、酢酸６００ｇを仕込み、８０℃まで昇温して３−メチル−２−ブタノン１０３．３ｇを滴下し、８０℃で１時間撹拌した後、８０℃で硫酸１９６．１ｇを滴下し、１０８℃で２時間反応させた。冷却後、反応液にトルエン８１６．８ｇを加え、２０重量％水酸化ナトリウム水溶液、水で洗浄し、無水硫酸ナトリウムで乾燥後、脱溶媒して得た粗結晶をエタノール２０４．２ｇで再結晶を行い２，３，３−トリメチル−５−ニトロインドレニン結晶６１．２ｇを得た。（収率３０％）
また、ベンゼンスルホニルクロリド１７６．６ｇ、２−フェネチルエタノール１４６．６ｇ、トルエン１０４９．３ｇを反応フラスコに仕込み、氷冷下でトリエチルアミン２０２．４ｇを１時間で滴下し、冷却化で１時間反応させた後、更に室温で１時間反応させた。再び氷浴下で冷却し、３５重量％塩酸水溶液、水で洗浄した後、無水硫酸ナトリウムで乾燥し、脱溶媒を行いベンゼンスルホン酸フェネチルエステル２１２．５ｇを得た。（収率８１％）
次に２，３，３−トリメチル−５−ニトロインドレニン２０．４ｇ、上記で得たベンゼンスルホン酸フェネチルエステル５２．４ｇを反応フラスコに仕込み、１３０℃で１時間反応させた後、８０℃で酢酸エチルを２３．３ｇ加えて晶析を行い１−フェネチル−２，３，３−トリメチル−５−ニトロインドレニンベンゼンスルホン酸塩１９．６ｇを得た。（収率４２％）
上記のスルホン酸塩４．７ｇ、フェロセンカルボキシアルデヒド２．１ｇ、ジメチルホルムアミド５．３ｇを反応フラスコに仕込み、１時間反応させた後テトラフルオロホウ酸ナトリウム２．２ｇとジメチルホルムアミド１０．６ｇを加え、８０℃で塩交換を行った。反応液からクロロホルム２０ｇで抽出した溶液を水洗、無水硫酸ナトリウムで乾燥後、脱溶媒して得られた粗結晶をヘキサン／酢酸エチル＝３／７（ｖｏｌ）溶媒、シリカゲルカラムにより精製し目的物結晶１．１ｇを得た。（収率１９％）
【００８８】
（分析結果）
ＵＶ吸収スペクトル；λmax ６７５ｎｍ（ε１．０×１０⁴ ）
ＰＭＲ吸収スペクトル（ｐｐｍ；多重度；Ｈ）
（１．７；ｓ；６）（２．４；ｔ；２）（４．３；ｓ；５）（４．５；ｔ；２）
（５．０；ｓ；２）（５．２；ｓ；２）（６．７；ｄ；１）
（７．１〜７．２；ｍ；５）（７．８；ｄ；１）（８．４；ｄ；１）
（８．５；ｓ；１）（８．６；ｄ；１）
ＭＳスペクトル：５９２（calc；５９２．２）
ＣＨＮ：Ｃ重量％；Ｈ重量％；Ｎ重量％
６０．４；４．８９；４．６９（calc；６０．８；４．９４；４．７３）
Ｆｅ分析：９．３８％（calc; ９．４３）
【００８９】
（製造例５）化合物Ｎｏ．１４のヨウ素塩の合成
反応フラスコに３，４−ジクロロフェニルヒドラジン塩酸塩２１３．５ｇ、酢酸２４０．２ｇを仕込み、８０℃まで昇温して３−メチル−２−ペンタノン１２０．２ｇを滴下し、１００℃で２時間反応させた。酢酸を脱溶媒した残渣からトルエン９６８．６ｇで抽出した溶液を水洗、無水硫酸ナトリウムで乾燥し、脱溶媒して得られた粗結晶をヘキサン／酢酸エチル＝３／７（ｖｏｌ）溶媒、シリカゲルカラムにより精製して３−エチル−２，３−ジメチル−４，５−ジクロロインドレニン６０．８ｇを得た。（収率２５％）
上記で得られた３−エチル−２，３−ジメチル−４，５−ジクロロインドレニン２４．２ｇ、３−フェニルプロピルアイオダイド４９．２ｇを反応フラスコに仕込み、１３０℃で２時間反応させた後、８０℃で酢酸エチルを４７．４ｇ加えて晶析を行い１−フェニルプロピル−２，３，３−トリメチル−４，５−ジクロロインドレニンヨウ素塩結晶２２．３ｇを得た（収率４７％）。
上記で得たヨウ素塩４．７ｇ、フェロセンカルボキシアルデヒド２．１ｇ、ジメチルホルムアミド６．７ｇを反応フラスコに仕込み、１時間反応させた反応液をクロロホルム２０ｇで抽出した溶液を、水洗、無水硫酸ナトリウムで乾燥後、脱溶媒した。得られた粗結晶をヘキサン／酢酸エチル＝３／７（ｖｏｌ）溶媒、シリカゲルカラムにより精製し目的物結晶１．１ｇを得た。（収率１６％）
【００９０】
（分析結果）
ＵＶ吸収スペクトル；λmax ６６０ｎｍ（ε０．９７×１０⁴ ）
ＰＭＲ吸収スペクトル（ｐｐｍ；多重度；Ｈ）
（１．０；ｔ；３）（１．６；ｍ；２）（１．７；ｓ；３）（１．９；ｃ；２）
（２．６；ｔ；２）（４．３；ｓ；５）（４．４；ｔ；２）（５．２；ｓ；２）
（５．３；ｓ；２）（６．８；ｄ；１）（７．１〜７．０；ｍ；５）
（８．２；ｓ；１）（８．４；ｓ；１）（８．５；ｄ；１）
ＭＳスペクトル：６８３（calc；６８３．１）
ＣＨＮ：Ｃ重量％；Ｈ重量％；Ｎ重量％
５５．８；４．７７；２．００（calc；５６．２；４．７１；２．０５）
Ｆｅ分析：８．１０％（calc; ８．１６）
【００９１】
実施例１〜３及び比較例１〜３
（熱的挙動の評価）
フェロセン誘導体化合物と色素との混合物（表１〜３）について示差熱分析装置を用いて熱的挙動の観察を行った。該混合物は熱により分解してピットを形成するが、分解挙動としては、分解温度域が狭く、シャープに分解するものがピット制御性に優れ、低温で分解するものほどエネルギー的に優位である。従って、ＴＧによる分解開始点（Ts）とＤＳＣによる分解のピークトップ（Tt）の温度幅及びピークの形状からピット制御性を評価し、分解温度の低下はＤＳＣによるピークトップの温度で評価した。
【００９２】
【表１】

【００９３】
【表２】

【００９４】
【表３】

【００９５】
実施例４及び比較例４
（光学記録媒体の製造及び耐光性評価）
表４及び表５に示す色素化合物とフェロセン誘導体化合物をテトラフルオロプロパノールに計１重量％溶解させ、この溶液を４０ｍｍ角のガラス上に１０００回転／分、３０秒でスピンコート塗布し、得られた資料を６０℃で３０分乾燥させ、光学記録媒体テストピースを作成した。
耐光性評価
上記により製造された各光学記録媒体テストピースにキセノン耐候性試験機（テーブルサン、スガ試験機（株）社製）を用いて、５００００ルクスの光を照射し、λmax における吸光度半減期（λmax における吸光度の値が、媒体作成時の５０％まで低下するのに要する時間）を測定した。その結果を表４及び表５に示す。
尚、表４及び表５における添加効果の数値は、添加剤（本発明に係るフェロセン誘導体化合物又は比較化合物１）及び色素化合物を使用した光学記録材料の吸光度半減期（Ａ）から、添加剤を使用せず且つ該色素化合物と同一の色素化合物のみを用いた光学記録材料の吸光度半減期（Ｂ）を引いたものである。
【００９６】
【表４】

【００９７】
【表５】

【００９８】
【発明の効果】
本発明の光学記録材料は、ピット制御性、低温分解性及び耐光性に優れたものである。
また、本発明の光学記録媒体は、可視及び赤外領域の波長を有し且つ低エネルギーのレーザー等により高密度の光学記録及び再生が可能なものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an optical recording material used for an optical recording medium for recording information by applying information as a thermal information pattern by a laser or the like, and an optical recording medium using the same, and more particularly, to wavelengths in the visible and infrared regions. And an optical recording material used for an optical recording medium capable of high-density optical recording and reproduction with a low-energy laser or the like, and an optical recording medium using the same.
[0002]
[Prior art and problems to be solved by the invention]
In general, the optical recording medium has a feature that the recording medium does not wear and deteriorate because the recording head does not contact the writing or reading head. In particular, the optical recording medium that gives information as thermal information does not require development processing in a dark room. The development has been actively conducted because of its advantages.
[0003]
Such an optical recording medium uses recording light as heat. For example, information can be recorded at high density by forming optically detectable pits on a thin recording layer provided on a substrate. Can do.
[0004]
Information is written on the recording medium by scanning a laser focused on the surface of the recording layer and forming pits in the recording layer that has absorbed the irradiated laser energy. In the information recorded on this recording medium, formed pits can be detected by reading light.
[0005]
Examples of the recording medium include an optical recording medium (CD-R) that can be written and reproduced by a near-infrared semiconductor laser having a wavelength of 770 to 830 nm corresponding to the compact disc (CD) standard, and a red semiconductor having a shorter wavelength of 620 to 690 nm. The laser beam spot is made smaller by using a laser to increase the recording density, and using a data compression technology, etc., it is in compliance with the DVD standard for large-capacity optical recording media (digital versatility discs, DVDs) that can record moving images. An optical recording medium (DVD-R) capable of additional recording or recording can be used. As a recording layer of such an optical recording medium, metal thin films such as an aluminum vapor deposition film, tellurium oxide thin films, bismuth thin films, and chalcogenide-based materials have been used so far. Inorganic optical recording materials such as amorphous glass films have been mainly used.
[0006]
These thin films are difficult to form by a coating method and need to be formed by sputtering or vacuum vapor deposition. However, the operation is complicated, and when the above inorganic material is used, it is difficult to form a laser beam. It has drawbacks such as high reflectivity, high thermal conductivity, and low utilization efficiency of laser light.
[0007]
For this reason, a method has been proposed in which an optical recording material mainly composed of an organic compound dye capable of forming pits with a semiconductor laser is used as a recording layer instead of an inorganic material.
[0008]
As these dyes, azo dyes, phthalocyanine dyes, and cyanine dyes are used. Among them, cyanine dyes composed of salts of cyanine dye cations such as indolenine, thiazole, imidazole, oxazole, quinoline, and selenazole and various anions are preferably used because of their high sensitivity. Indolenine-based indocyanine dyes are more preferably used because of their particularly high sensitivity.
[0009]
However, when the above organic compound dyes are used in optical recording materials, the pit formation characteristics, pit controllability, and light stability may not be sufficient by themselves, and these problems become important as the recording medium capacity increases. It has become.
[0010]
In response to the above problems, use of various additives for imparting functions such as pit formation promoting property, pit controllability, and light stability has been studied. For example, in Japanese Patent Application Laid-Open Nos. 07-99887, 10-291366, and 11-86337, the use of metallocenes and metal β-diketonates is described in Japanese Patent Publication No. 01-034464 and Japanese Patent Publication No. 01. No. 034465 describes the use of complex compounds called quenchers.
[0011]
However, these additives have not been able to obtain a sufficient effect with respect to the above-mentioned problems, and sometimes have deteriorated recording characteristics such as sensitivity.
[0012]
Accordingly, an object of the present invention is to provide an optical recording material having improved pit formability, pit controllability, light stability, etc., used for a recording layer of an optical recording medium, and an optical recording medium using the same. There is.
[0013]
[Means for Solving the Problems]
As a result of repeated studies, the present inventors have found that the above object can be achieved by using a metallocene derivative compound having an indolenine skeleton, which is a novel compound.
[0014]
  The present invention has been made based on the above findings, and3]General formula of(I ' )An optical recording material comprising a compound represented by the formula:In detail, an optical recording material comprising a compound represented by the general formula (I) of the following [Chemical Formula 6] (same as the above [Chemical Formula 1])Is to provide.
[0015]
[Chemical Formula 3]

[Formula 4]

[0016]
The present invention also provides an optical recording medium, wherein a thin film containing the optical recording material is formed as a recording layer on a substrate.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the optical recording material of the present invention will be described in detail.
[0018]
The compound represented by the above general formula (I) used in the optical recording material of the present invention is a novel compound and is a function-imparting additive used in a recording layer of an optical recording medium described later.
[0019]
  General formula above(I ' )R in ring A₁As the halogen atom represented by, for example, fluorine, chlorine, bromine and iodine can be mentioned, and as the alkyl group having 1 to 4 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl , Tertiary butyl and the like, and examples of the alkoxy group having 1 to 4 carbon atoms include groups derived from the above alkyl groups., RThe organic group having 1 to 30 carbon atoms represented by the formula is not particularly limited and may contain a branch, an unsaturated bond, an ether bond, an aryl group, or the like, and a substituent such as a halogen atom, a cyano group, or a nitro group. The alkylidene group having 1 to 6 carbon atoms represented by Y includes methylidene, dimethylmethylidene, ethylmethylmethylidene, diethylmethylidene, methylpropylmethylidene, and ethylpropyl. Examples of the cycloalkylidene having 3 to 6 carbon atoms include cyclopropane-1,1-diyl, cyclobutane-1,1-diyl, 2,4-dimethylcyclobutane-1,1-diyl, 3- Examples thereof include dimethylcyclobutane-1,1-diyl, cyclopentane-1,1-diyl, cyclohexane-1,1-diyl, and the like. Examples of the alkyl group in the nitrogen atom having an alkyl group include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, tertiary Examples include octyl and 2-ethylhexyl.
[0020]
  General formula above(I ' )In An^m-The anion represented by the formula is not particularly limited, but for example, halogen anions such as chlorine anion, bromine anion, iodine anion, fluorine anion; perchlorate anion, chlorate anion, thiocyanate anion, phosphorus hexafluoride anion , Inorganic anions such as antimony hexafluoride anion, boron tetrafluoride anion, organic sulfonate anions such as benzenesulfonate anion toluenesulfonate anion, trifluoromethanesulfonate anion; octyl phosphate anion, dodecyl phosphate anion, octadecyl phosphorus Organic phosphate anions such as acid anion, phenyl phosphate anion, nonylphenyl phosphate anion, 2,2′-methylenebis (4,6-ditert-butylphenyl) phosphonate anion, quencher anion described later, and the like And As those of valence, such as benzene disulfonic acid anion and naphthalene disulfonic acid anion.
[0021]
  In addition, the above general formula(I ' )The metallocene group represented by X isA ferrocene group represented by the following [Chemical Formula 5]:Publicly knownFerroceneIntroducing from a compoundwear.
[0022]
[Chemical formula 5]

[0024]
  General formula above(I ' )The compound represented by,For more informationThe following [Chemical 6] (the above [Chemical1General formula of(I)Compound represented byAnd the compound isIt is preferable in terms of cost and performance.
[0025]
[Chemical 6]

[0026]
  General formula above(I)R₁, R, Y, and An^m-As the above general formula(I ' )The same thing is mentioned.
[0027]
  General formula above(I)Specific examples of the compound represented by the following compound No. 1-No. 8 etc. are mentioned. In the following examples, the anion is omitted from the cation.
[0028]
[Chemical 7]

[0029]
[Chemical 8]

[0030]
[Chemical 9]

[0031]
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[0032]
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[0033]
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[0034]
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[0035]
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[0036]
  As more preferred compounds, the above general formula (I)DuringThe group represented by Y is an alkylidene group having 1 to 6 carbon atoms or a cycloalkylidene group having 3 to 6 carbon atoms, and an organic group represented by R is the following [Chemical 15]2General formula of( II )The ferrocene compound which is group represented by these is mentioned.
[0037]
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[0038]
  General formula above( II )R₂As a C1-C4 alkylene group represented by these, methylene, ethylene, propylene, 1-methylethylene, 2-methylethylene, butylene etc. are mentioned, for example, R_ThreeAs the alkyl group having 1 to 4 carbon atoms represented by the above general formula (I)DuringR₁The same groups as those described above are exemplified, and examples of the alkenyl group having 2 to 4 carbon atoms include vinyl, propenyl, isopropenyl, butenyl and the like, and R_ThreeExamples of the halogen atom which is a substituent of the phenyl group in the group include fluorine, chlorine, bromine and iodine, and R_ThreeExamples of the alkyl group or alkoxy group having 1 to 4 carbon atoms, which is a substituent of the phenyl group therein, include the general formula (I)DuringR₁The same group is mentioned.
[0039]
Specific examples of the more preferable compounds described above include the following compound Nos. 9-No. 14 etc. are mentioned. In the following examples, the anion is omitted from the cation.
[0040]
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[0041]
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[0042]
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[0043]
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[0044]
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[0045]
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[0046]
The method for producing a suitable ferrocene derivative compound represented above is not particularly limited, but for example, it is synthesized by the route shown in the following [Chemical Formula 22].
[0047]
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[0048]
The compound (metallocene derivative compound) represented by the above general formula (I), which is a novel compound used in the present invention, has the following properties and is an excellent compound as a multifunctional additive for optical recording materials. .
(1) It functions as a light stabilizer.
Prevents the dye from fading due to natural light and gives the recording material light resistance.
(2) It functions as a pit formation accelerator.
This has the effect of shifting the pit formation temperature of the dye layer to the low temperature side.
(3) It functions as a pit control agent.
Since a clear threshold value for pit formation is given with respect to temperature, sharp pits can be formed.
(4) There is no volatility.
Since it is not volatile, it has excellent safety and quality stability during recording layer formation.
[0049]
In the optical recording material of the present invention, a dye is usually used, and the dye is not particularly limited as long as it is an organic compound-based dye that can form pits by a semiconductor laser. An azo dye or a phthalocyanine dye Any known dyes such as cyanine dyes can be used, but cyanine dyes are preferable, and among them, indocyanine dyes are more preferable because they provide an excellent additive effect.
[0050]
Specific examples of particularly preferable pigments include the following compound No. 15-23 etc. are mentioned. In the following examples, the anion is omitted from the cation.
[0051]
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[0052]
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[0053]
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[0054]
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[0055]
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[0056]
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[0057]
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[0058]
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[0059]
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[0060]
The optical recording material of the present invention contains the above metallocene derivative compound [compound represented by the above general formula (I)] as an essential component, preferably contains both a dye and the above metallocene derivative compound, It is applied as a recording layer of an optical recording medium such as LD, CD, DVD, CD-R, DVD-R.
[0061]
In the optical recording material of the present invention, the ratio of the dye to the metallocene derivative compound is preferably 0.01% by weight or more, since the effect is difficult to obtain when the metallocene derivative compound is less than 0.01% by weight with respect to the dye. When used as a recording layer for CD-R and DVD-R, 0.1 to 20% by weight is preferable.
[0062]
Next, the optical recording medium of the present invention will be described in detail.
The optical recording medium of the present invention is obtained by forming a thin film containing the above-described optical recording material of the present invention as a recording layer on a substrate.
For forming the recording layer in the optical recording medium of the present invention, a conventionally known method can be used. Generally, lower alcohols such as methanol and ethanol, ether alcohols such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, and butyl diglycol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, ethyl acetate, Esters such as butyl acetate and methoxyethyl acetate, acrylic esters such as ethyl acrylate and butyl acrylate, fluorinated alcohols such as 2,2,3,3-tetrafluoropropanol, benzene, toluene and xylene It can be easily formed by applying a solution in which the optical recording material is dissolved in an organic solvent such as hydrocarbons, chlorinated hydrocarbons such as methylene dichloride, dichloroethane and chloroform onto the substrate.
[0063]
The thickness of the recording layer is usually 0.001 to 10 [mu] m, preferably 0.01 to 5 [mu] m. The method for forming the recording layer is not particularly limited, and for example, a commonly used method such as a spin coating method can be used.
[0064]
When the recording layer in the optical recording medium of the present invention contains the optical recording material, the amount of the recording layer used is preferably 50 to 100% by weight in combination with the dye and the metallocene derivative compound.
[0065]
Further, the recording layer in the optical recording medium of the present invention may contain, in addition to the optical recording material, resins such as polyethylene, polyester, polystyrene, polycarbonate, and the like, if necessary. An inhibitor, a lubricant, a flame retardant, a light stabilizer, a dispersant, an antioxidant, a crosslinking agent and the like may be contained.
[0066]
Furthermore, the recording layer may contain an aromatic nitroso compound, a bisiminium salt, a transition metal chelate compound, or the like as a quencher such as singlet oxygen. As these compounds, for example, known compounds as proposed in JP-A-59-55795 and JP-A-60-234892 are used, and preferably 0 to 50% by weight with respect to the recording layer. Used in the range of%.
[0067]
Representative examples of the quencher include compounds represented by the following general formulas (A) to (I) of [Chemical Formula 32] to [Chemical Formula 40].
[0068]
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[0069]
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[0070]
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[0071]
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[0072]
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[0073]
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[0074]
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[0075]
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[0076]
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[0077]
The material of the substrate on which such a recording layer is provided is not particularly limited as long as it is substantially transparent to writing light and reading light. For example, a resin such as polymethyl methacrylate, polyethylene terephthalate, and polycarbonate is used. Glass or the like is used. Moreover, the shape can use arbitrary shapes, such as a tape, a drum, a belt, a disk, according to a use.
[0078]
In addition, a reflective film can be formed on the recording layer by vapor deposition or sputtering using gold, silver, aluminum, copper or the like, or a protective layer made of acrylic resin, ultraviolet curable resin, or the like. You can also.
[0079]
Specific examples of the optical recording medium of the present invention include optical disks such as LD, CD, DVD, CD-R, and DVD-R.
[0080]
【Example】
Hereinafter, the present invention will be described in more detail with reference to production examples, examples, evaluation examples, and comparative examples. However, the present invention is not limited by the following examples.
[0081]
(Production Example 1) Compound No. 9 Production of phosphorus hexafluoride
A reaction flask was charged with 35.4 g of benzenesulfonyl chloride, 33.2 g of 2-phenoxyethanol, and 222.4 g of toluene, and 40.4 g of triethylamine was added dropwise over 1 hour under ice cooling. After reacting for 1 hour under cooling, the mixture was further reacted at room temperature for 1 hour, washed with water, dried over anhydrous sodium sulfate, and desolvated. The resulting crude crystals were recrystallized with 55.6 g of ethanol, and benzene 47.2 g crystals of sulfonic acid phenoxyethyl ester were obtained. (Yield 85%)
Next, 23.9 g of 2,3,3-trimethylindolenine, 41.7 g of the benzenesulfonic acid phenoxyethyl ester obtained above, and 131.2 g of 1-butanol were charged into a reaction flask and reacted at 120 ° C. for 3 hours. , Cooling and filtration, and ethanol washing. 93.8 benzene sulfonate crystals were obtained. (Yield 82%)
4.4 g of the benzene sulfonate obtained above, 2.1 g of ferrocenecarboxaldehyde, 6.2 g of dimethylformamide were charged into a reaction flask and reacted for 1 hour, 3.7 g of potassium hexafluorophosphate, 12.4 g of dimethylformamide. The salt was exchanged at 80 ° C. for 1 hour. The solution extracted with 20 g of chloroform from the reaction system was washed with water, dried over anhydrous sodium sulfate, and then the solvent was removed. The resulting crude crystals were purified with a hexane / ethyl acetate = 3/7 (vol) solvent, silica gel column. 1.2 g of product crystals were obtained. (Yield 20%)
[0082]
(result of analysis)
UV absorption spectrum: λmax 640 nm (ε1.1 × 10^Four)
PMR absorption spectrum (ppm; multiplicity; H)
(1.8; s; 6) (4.4; s; 5) (4.5; t; 2) (4.8; t; 2)
(5.0; s; 2) (5.1; s; 2) (6.7; d; 2) (6.9; t; 1)
(7.0: d; 1) (7.2; t; 2) (7.4 to 7.6; m; 3)
(7.6; d; 1) (8.3; d; 1)
MS spectrum: 621 (calc; 621.3)
CHN: C wt%; H wt%; N wt%
58.0; 4.81; 2.14 (calc; 58.0; 4.87; 2.25)
Fe analysis: 8.88% (calc; 8.99)
[0083]
(Production Example 2) Compound No. Synthesis of 10 iodine salts
A reaction flask was charged with 31.6 g of β-naphthylhydrazine and 48.0 g of acetic acid, heated to 80 ° C., 20.7 g of 3-methyl-2-butanone was added dropwise, and the mixture was reacted at 100 ° C. for 2 hours. Was desolvated. The solution extracted from the residue with 167.4 g of toluene was washed with a 20 wt% aqueous sodium hydroxide solution and water, dried over anhydrous sodium sulfate and then desolvated, and then the crude crystals were recrystallized with 41.8 g of toluene, 2,3.4 g of 3,3-trimethylbenzoindolenine was obtained. (Yield 56%)
Next, 20.9 g of 2,3,3-trimethylbenzoindolenine obtained above and 39.6 g of isoamyl iodide were charged into a reaction flask, reacted at 120 ° C. for 3 hours, and then ethyl acetate 20 at 80 ° C. .4 g was added, and crystallization was performed to obtain 31.3 g of 1-isoamyl-2,3,3-trimethylbenzoindolenine iodine salt. (Yield 77%)
4.1 g of the iodine salt obtained above, 2.1 g of ferrocenecarboxaldehyde and 6.0 g of dimethylformamide were charged into a reaction flask and reacted for 1 hour to obtain crude crystals of hexane / ethyl acetate = 3/7 (vol). Purification by a solvent and a silica gel column gave 0.7 g of the desired product crystal. (Yield 12%)
[0084]
(result of analysis)
UV absorption spectrum: λmax 637 nm (ε1.0 × 10^Four)
PMR absorption spectrum (ppm; multiplicity; H)
(1.1; d; 6) (1.8-1.9; m; 3) (1.9; s; 6)
(4.4; s; 5) (4.8; t; 2) (5.0; s; 2) (5.3; s; 2)
(7.2: d; 1) (7.6 to 7.7; m; 3) (8.0 to 8.1; m; 3) (8.6; d; 1)
MS spectrum: 603 (calc; 603.4)
CHN: C wt%; H wt%; N wt%
61.4; 5.61; 2.35 (calc; 61.7; 5.68; 2.32)
Fe analysis: 9.30% (calc; 9.25)
[0085]
(Production Example 3) Compound No. Synthesis of 11 perchlorates
A reaction flask was charged with 27.6 g of 4-methoxyphenylhydrazine and 48.0 g of acetic acid, heated to 80 ° C., 20.7 g of 3-methyl-2-butanone was added dropwise, and reacted at 100 ° C. for 2 hours. Acetic acid was desolvated. A solution extracted from the residue with 151.2 g of toluene was washed with a 20 wt% aqueous sodium hydroxide solution and water, dried over anhydrous sodium sulfate, desolvated, and 22.6 g of 2,3,3-trimethyl-5-methoxyindolenine. Got. (Yield 60%)
Next, 18.9 g of 2,3,3-trimethyl-5-methoxyindolenine obtained above and 33.8 g of propyl iodide were charged and reacted at 100 ° C. for 3 hours. Crystallization was performed by adding 0 g to obtain 26.6 g of crystals of 1-propyl-2,3,3-trimethyl-5-methoxyindolenin iodine salt. (Yield 74%)
3.6 g of the iodine salt obtained above, 2.1 g of ferrocenecarboxaldehyde and 5.3 g of dimethylformamide were charged into a reaction flask and reacted for 1 hour, and then 11.2 g of sodium perchlorate monohydrate 2.8 g of methanol. The solution was added and salt exchange was performed at 70 ° C. for 1 hour. A solution extracted with 20 g of chloroform from the reaction solution was washed with water, dried over anhydrous sodium sulfate, and the solvent was removed. The resulting crude crystals were purified with a hexane / ethyl acetate = 3/7 (vol) solution, silica gel column to obtain target crystals. 0.8 g was obtained. (Yield 15%)
[0086]
(result of analysis)
UV absorption spectrum: λmax 625 nm (ε0.93 × 10^Four)
PMR absorption spectrum (ppm; multiplicity; H)
(1.0; t; 3) (1.9; s; 6) (2.0; m; 2) (3.9; s; 3)
(4.3; s; 5) (4.4; t; 2) (5.0; s; 2) (5.1; s; 2)
(6.9; d; 1) (7.0; m; 2) (7.5: d; 1) (8.2; d; 1)
MS spectrum: 527 (calc; 527.8)
CHN: C wt%; H wt%; N wt%
58.9; 5.69; 2,66 (calc; 59.2; 5.73; 2.65)
Fe analysis: 10.3% (calc; 10.6)
[0087]
(Production Example 4) Compound No. Synthesis of 12 boron tetrafluoride salts
A reaction flask was charged with 153.1 g of 4-nitrophenylhydrazine and 600 g of acetic acid, heated to 80 ° C., 103.3 g of 3-methyl-2-butanone was added dropwise, stirred at 80 ° C. for 1 hour, and then at 80 ° C. 196.1 g of sulfuric acid was added dropwise and reacted at 108 ° C. for 2 hours. After cooling, 816.8 g of toluene was added to the reaction solution, washed with a 20 wt% aqueous sodium hydroxide solution and water, dried over anhydrous sodium sulfate, and the solvent was removed. The resulting crude crystals were recrystallized with 204.2 g of ethanol. As a result, 61.2 g of 2,3,3-trimethyl-5-nitroindolenine crystals were obtained. (Yield 30%)
In addition, 176.6 g of benzenesulfonyl chloride, 146.6 g of 2-phenethylethanol, and 1049.3 g of toluene were charged into a reaction flask, and 202.4 g of triethylamine was added dropwise over 1 hour under ice cooling, and the reaction was allowed to proceed for 1 hour by cooling. Thereafter, the mixture was further reacted at room temperature for 1 hour. The mixture was cooled again in an ice bath, washed with a 35 wt% aqueous hydrochloric acid solution and water, dried over anhydrous sodium sulfate, and desolvated to obtain 212.5 g of benzenesulfonic acid phenethyl ester. (Yield 81%)
Next, 20.4 g of 2,3,3-trimethyl-5-nitroindolenine and 52.4 g of the benzenesulfonic acid phenethyl ester obtained above were charged into a reaction flask and reacted at 130 ° C. for 1 hour, then at 80 ° C. Crystallization was performed by adding 23.3 g of ethyl acetate to obtain 19.6 g of 1-phenethyl-2,3,3-trimethyl-5-nitroindolenine benzenesulfonate. (Yield 42%)
4.7 g of the above sulfonate, 2.1 g of ferrocenecarboxaldehyde, and 5.3 g of dimethylformamide were charged into a reaction flask and reacted for 1 hour, and then 2.2 g of sodium tetrafluoroborate and 10.6 g of dimethylformamide were added. Salt exchange was performed at 80 ° C. A solution extracted with 20 g of chloroform from the reaction solution was washed with water, dried over anhydrous sodium sulfate, and then the solvent was removed. The resulting crude crystals were purified by hexane / ethyl acetate = 3/7 (vol) solvent, silica gel column to obtain target crystals. 1.1 g was obtained. (Yield 19%)
[0088]
(result of analysis)
UV absorption spectrum: λmax 675 nm (ε1.0 × 10^Four)
PMR absorption spectrum (ppm; multiplicity; H)
(1.7; s; 6) (2.4; t; 2) (4.3; s; 5) (4.5; t; 2)
(5.0; s; 2) (5.2; s; 2) (6.7; d; 1)
(7.1-7.2; m; 5) (7.8; d; 1) (8.4; d; 1)
(8.5; s; 1) (8.6; d; 1)
MS spectrum: 592 (calc; 592.2)
CHN: C wt%; H wt%; N wt%
60.4; 4.89; 4.69 (calc; 60.8; 4.94; 4.73)
Fe analysis: 9.38% (calc; 9.43)
[0089]
(Production Example 5) Compound No. Synthesis of 14 iodine salts
A reaction flask was charged with 213.5 g of 3,4-dichlorophenylhydrazine hydrochloride and 240.2 g of acetic acid, heated to 80 ° C., 120.2 g of 3-methyl-2-pentanone was added dropwise, and the mixture was reacted at 100 ° C. for 2 hours. It was. A solution extracted with 968.6 g of toluene from the residue obtained by removing the solvent from acetic acid was washed with water, dried over anhydrous sodium sulfate, and the crude crystals obtained by removing the solvent were treated with hexane / ethyl acetate = 3/7 (vol) solvent, silica gel column. To obtain 60.8 g of 3-ethyl-2,3-dimethyl-4,5-dichloroindolenine. (Yield 25%)
After charging 24.2 g of 3-ethyl-2,3-dimethyl-4,5-dichloroindolenine and 49.2 g of 3-phenylpropyl iodide obtained above in a reaction flask and reacting at 130 ° C. for 2 hours Then, 47.4 g of ethyl acetate was added at 80 ° C. for crystallization to obtain 22.3 g of 1-phenylpropyl-2,3,3-trimethyl-4,5-dichloroindolenin iodine salt crystals (yield 47%). ).
A solution obtained by adding 4.7 g of the iodine salt obtained above, 2.1 g of ferrocenecarboxaldehyde, and 6.7 g of dimethylformamide to a reaction flask and extracting the reaction solution reacted for 1 hour with 20 g of chloroform was washed with water and anhydrous sodium sulfate. After drying, the solvent was removed. The obtained crude crystals were purified with a hexane / ethyl acetate = 3/7 (vol) solvent, silica gel column to obtain 1.1 g of the desired crystals. (Yield 16%)
[0090]
(result of analysis)
UV absorption spectrum: λmax 660 nm (ε0.97 × 10^Four)
PMR absorption spectrum (ppm; multiplicity; H)
(1.0; t; 3) (1.6; m; 2) (1.7; s; 3) (1.9; c; 2)
(2.6; t; 2) (4.3; s; 5) (4.4; t; 2) (5.2; s; 2)
(5.3; s; 2) (6.8; d; 1) (7.1-7.0; m; 5)
(8.2; s; 1) (8.4; s; 1) (8.5; d; 1)
MS spectrum: 683 (calc; 683.1)
CHN: C wt%; H wt%; N wt%
55.8; 4.77; 2.00 (calc; 56.2; 4.71; 2.05)
Fe analysis: 8.10% (calc; 8.16)
[0091]
Examples 1-3 and Comparative Examples 1-3
(Evaluation of thermal behavior)
The thermal behavior of the mixture (Tables 1 to 3) of the ferrocene derivative compound and the dye was observed using a differential thermal analyzer. The mixture decomposes by heat to form pits, but the decomposition behavior is narrow in the decomposition temperature range, sharp decomposition is excellent in pit controllability, and the decomposition at low temperature is superior in energy. Therefore, the pit controllability was evaluated from the temperature range and peak shape of the decomposition start point (Ts) by TG and the peak top (Tt) of decomposition by DSC, and the decrease in decomposition temperature was evaluated by the temperature of the peak top by DSC.
[0092]
[Table 1]

[0093]
[Table 2]

[0094]
[Table 3]

[0095]
Example 4 and Comparative Example 4
(Manufacture of optical recording media and evaluation of light resistance)
The dye compound and the ferrocene derivative compound shown in Table 4 and Table 5 were dissolved in tetrafluoropropanol in a total of 1% by weight, and this solution was spin-coated on a 40 mm square glass at 1000 rpm for 30 seconds. The material was dried at 60 ° C. for 30 minutes to prepare an optical recording medium test piece.
Light resistance evaluation
Each optical recording medium test piece manufactured as described above was irradiated with light of 50000 lux using a xenon weathering tester (Table Sun, manufactured by Suga Test Instruments Co., Ltd.), and the absorbance half-life at λmax (at λmax) The time required for the absorbance value to decrease to 50% at the time of preparation of the medium was measured. The results are shown in Tables 4 and 5.
In addition, the numerical value of the additive effect in Table 4 and Table 5 is based on the absorbance half-life (A) of the optical recording material using the additive (ferrocene derivative compound or comparative compound 1 according to the present invention) and the dye compound. The absorbance half-life (B) of an optical recording material that is not used and that uses only the same dye compound as the dye compound is subtracted.
[0096]
[Table 4]

[0097]
[Table 5]

[0098]
【The invention's effect】
The optical recording material of the present invention is excellent in pit controllability, low-temperature decomposability and light resistance.
The optical recording medium of the present invention has visible and infrared wavelengths, and can be recorded and reproduced with high density by a low energy laser or the like.

Claims (4)

Optical recording material characterized by containing the general formula (I) compound represented by the below Symbol Chemical Formula 1].

Said Y is cycloalkylidene group having 3 to 6 alkylidene group, or a carbon number of 1 to 6 carbon atoms, said R is according to claim 1, wherein a group represented by the following general formula [Formula 2] (II) Optical recording material.

The optical recording material according to claim 1 or 2, comprising one or more dyes selected from azo dyes, phthalocyanine dyes, and cyanine dyes. An optical recording medium, wherein a thin film containing the optical recording material according to any one of claims 1 to 3 is formed as a recording layer on a substrate.